The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan coupler, and to a novel pyrrolotriazole compound and a dye-forming compound.
It is well known that, in a silver halide color photographic light-sensitive material, an aromatic primary amine color-developing agent, oxidized by the exposed silver halide, which is an oxidizing agent, reacts with a coupler to form a dye, such as indophenols, indoanilines, indamines, azomethines, phenoxazines, and phenazines, thereby forming a dye image. In this photography, a subtractive color photography is employed, and a dye image is formed by yellow, magenta, and cyan dyes. Hitherto, in order to form a cyan dye among these dyes, phenol or naphthol couplers have generally been used. However, these couplers have the serious problem that dyes obtained from these couplers have an undesirable absorption in the green region, which results in conspicuous deterioration of color reproduction. Accordingly, it is strongly desired to resolve this problem.
As a means for resolving this problem, use of the heterocyclic compounds described in, for example, U.S. Pat. Nos. 4,728,598 and 4,873,183, European Patent No. 249453 A2, is proposed. However, these couplers have such fatal problems as low coupling activity. As a coupler that has overcome these problems, pyrroloazole couplers described in, for example, European Patent Nos. 0491197 A1, 0488248, 0545300, 0628867 A1, and 0484909; U.S. Pat. No. 5,164,289, and JP-A-6-347960 (xe2x80x9cJP-Axe2x80x9d means unexamined published Japanese patent application), are proposed. These couplers are excellent in both hue of the resulting dye and coupling activity. Further, they are also excellent in the point that the molecular extinction coefficient of the resulting dye is high.
However, there is a problem that dyes obtained from these pyrroloazole couplers are apt to cause aggregation in a film, which results in a difference in hue between a high density portion and a low density portion. This problem is especially remarkable when the amount of a high-boiling-point organic solvent (oil) to be used when emulsifying is small.
As a means of resolving this problem, pyrroloazole couplers described in JP-A-9-189988 and JP-A-10-198012 are proposed. Although the dye image obtained from these pyrroloazole couplers is indeed excellent in hue, the color reproduction ranging from the green color to the blue color region is not yet satisfactory. That is, since the extinction coefficient of the cyan dye image in the magenta region, which is not wanted therefor, is large, there is dissatisfaction with the current strong demand for pictures that exhibit more excellent color reproduction.
Further, the dye image obtained from these pyrroloazole couplers is not satisfactory in fastness to light, so that further improvement has been demanded.
Further, when these known pyrroloazole couplers are used, serious problems arise as to the occurrence of both color mixing and stain on the white background. The term xe2x80x9ccolor mixingxe2x80x9d means that an oxidation product of the aromatic primary amine color-developing agent produced in another layer (for example, a magenta layer), diffuses into a cyan-color forming layer containing a pyrrolotriazole coupler, and reacts with said pyrrolotriazole coupler upon a coupling reaction, thereby causing an undesired cyan-color forming. The term xe2x80x9cstain on the white backgroundxe2x80x9d means that, at the unexposed portion, which originally should form a white background, an oxidation product of the developing agent produced by oxidation (for example, air oxidation) of a developing agent slightly remaining in a film of the color photograph after processing, reacts with a cyan coupler upon a coupling reaction, thereby also causing an undesired cyan-color forming (coloration). Therefore, improvement of both of these problems has been strongly demanded from the viewpoint of color reproduction.
On the other hand, in addition to the foregoing silver halide color photographic light-sensitive material, development of compounds capable of providing excellent hue of the resulting dye and light-fastness as mentioned above, especially dye-forming compounds, is strongly demanded in the industry in which dyes, especially dyes for an image, are used.
The present invention is a silver halide color photographic light-sensitive material that contains a cyan coupler represented by the following formula (I): 
wherein R1 and R2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, or R1 and R2 may bond together to form a 5- or 6-membered nitrogen-containing heterocycle; R3 represents an alkyl group, a cycloalkyl group or an alkenyl group; R5 represents an alkyl group or an aryl group; and R4, R6, R7 and R8 each independently represent a hydrogen atom or a substituent, with the proviso that at least one of R4, R6, R7 and R8 represents a substituent, and that two groups of R4 to R8, which adjoin each other, do not bond together to form any ring.
Further the present invention is a pyrrolotriazole compound represented by the above formula (I).
Still further the present invention is a dye-forming compound represented by the above formula (I).
Other and further features and advantages of the invention will appear more fully from the following description.
As a result of intensive studies for attaining the foregoing task, the present inventors have found a novel pyrrolotriazole compound that can be used as a dye-forming compound.
According to the present invention, there are provided the following means:
(1) A silver halide color photographic light-sensitive material containing a cyan coupler represented by the following formula (I): 
wherein R1 and R2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, or R1 and R2 may bond together to form a 5- or 6-membered nitrogen-containing heterocycle; R3 represents an alkyl group, a cycloalkyl group or an alkenyl group; R5 represents an alkyl group or an aryl group; and R4, R6, R7 and R8 each independently represent a hydrogen atom or a substituent, with the proviso that at least one of R4, R6, R7 and R8 represents a substituent, and that two groups of R4, R5, R6, R7 and R8, which adjoin each other, do not bond together to form any ring.
(2) A pyrrolotriazole compound represented by the following formula (I): 
wherein R1 and R2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, or R1 and R2 may bond together to form a 5- or 6-membered nitrogen-containing heterocycle; R3 represents an alkyl group, a cycloalkyl group or an alkenyl group; R5 represents an alkyl group or an aryl group; and R4, R6, R7 and R8 each independently represent a hydrogen atom or a substituent, with the proviso that at least one of R4, R6, R7 and R8 represents a substituent, and that two groups of R4, R5, R6, R7 and R8, which adjoin each other, do not bond together to form any ring.
(3) A dye-forming compound represented by the following formula (I): 
wherein R1 and R2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, or R1 and R2 may bond together to form a 5- or 6-membered nitrogen-containing heterocycle; R3 represents an alkyl group, a cycloalkyl group or an alkenyl group; R5 represents an alkyl group or an aryl group; and R4, R6, R7 and R8 each independently represent a hydrogen atom or a substituent, with the proviso that at least one of R4, R6, R7 and R8 represents a substituent, and that two groups of R4, R5, R6, R7 and R8, which adjoin each other, do not bond together to form any ring.
The pyrrolotriazole compound represented by formula (I), which is defined in the foregoing item (2) in the present invention, can be used in the silver halide color photographic light-sensitive material for forming a dye image, which is defined in the foregoing item (1). Further, the pyrrolotriazole compound of formula (I) can be used as a dye-forming compound that is defined in the foregoing item (3).
The present invention will be described in detail below.
As to the substituent on formula (I) according to the present invention, the substituent including the group of substituents described below is defined as the term xe2x80x9cR40xe2x80x9d in this specification.
Namely, examples of the above-described group of substituents include a halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group (preferably straight-chain or branched-chain alkyl groups having 1 to 40 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl), a cycloalkyl group (preferably cycloalkyl groups having 3 to 40 carbon atoms, e.g., cyclopropyl, 1-ethylcyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably alkenyl groups having 2 to 40 carbon atoms, e.g., vinyl, allyl, 3-butene-1-yl), an aryl group (preferably aryl groups having 6 to 32 carbon atoms, e.g., phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably 5- to 8-membered heterocyclic groups having 1 to 32 carbon atoms, more preferably having at least one ring-constituting atom selected from nitrogen, oxygen and sulfur atoms, e.g., 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazole-2-yl), a cyano group, a silyl group (preferably silyl groups having 3 to 40 carbon atoms, e.g., trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), a hydroxyl group, a carbxyl group, a nitro group, an alkoxy group (preferably alkoxyl groups having 1 to 40 carbon atoms, e.g., methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy), a cycloalkyloxy group (preferably cycloalkyloxy groups having 3 to 8 carbon atoms, e.g., cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably aryloxy groups having 6 to 40 carbon atoms, e.g., phenoxy, 2-naphthoxy), a herocyclic oxy group (preferably heterocyclic oxy groups having 1 to 40 carbon atoms, more preferably those having the heterocyclic moiety as described for the above heterocyclic group, e.g., 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), a silyloxy group (preferably silyloxy groups having 1 to 40 carbon atoms, e.g., trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably acyloxy groups having 2 to 40 carbon atoms, e.g., acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably alkoxycarbonyloxy groups having 2 to 40 carbon atoms, e.g., ethoxycarbonyloxy, t-butoxycarbonyloxy), a cycloalkyloxycarbonyloxy group (preferably cycloalkyloxycarbonyloxy groups having 4 to 40 carbon atoms, e.g., cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably aryloxycarbonyloxy groups having 7 to 40 carbon atoms, e.g., phenoxycarbonyloxy), a carbamoyloxy group (preferably carbamoyloxy groups having 1 to 40 carbon atoms, e.g., N,N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably sulfamoyloxy groups having 1 to 40 carbon atoms, e.g., N,N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkanesulfonyloxy group (preferably alkanesulfonyloxy groups having 1 to 40 carbon atoms, e.g., methanesulfonyloxy, hexadecanesulfonyloxy), an arylsulfonyloxy group (preferably arylsulfonyl oxy groups having 6 to 40 carbon atoms, e.g., benzenesulfonyloxy), an acyl group (preferably acyl groups having 1 to 40 carbon atoms, e.g., formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl), an alkoxycarbonyl group (preferably alkoxycarbonyl groups having 2 to 40 carbon atoms, e.g., methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl), a cycloalkyloxycarbonyl group (preferably cycloalkyloxycarbonyl groups having 4 to 40 carbon atoms, e.g., cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably aryloxycarbonyl groups having 7 to 40 carbon atoms, e.g., phenoxycarbonyl), a carbamoyl group (preferably carbamoyl groups having 1 to 40 carbon atoms, e.g., carbamoyl, N,N-dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl), an amino group {an unsubstituted amino group, an alkylamino group, an anilino group and a heterocyclic amino group are included, for example, an unsubstituted amino group, an alkylamino group (preferably alkylamino groups having 1 to 32 carbon atoms, e.g., methylamino, N,N-dioctylamino, tetradecylamino, octadecylamino), an anilino group (preferably anilino groups having 6 to 40 carbon atoms, e.g., anilino, N-methylanilino), a heterocyclic amino group (preferably heterocyclic amino groups having 1 to 40 carbon atoms, more preferably those having the heterocyclic moiety as described for the above heterocyclic group, e.g., 4-pyridylamino)}, a carbonamido group (preferably carbonamido groups having 2 to 40 carbon atoms, e.g., acetoamido, benzamido, tetradecaneamido), a ureido group (preferably ureido groups having 1 to 40 carbon atoms, e.g., ureido, N,N-dimethyluredo, N-phenylureido), an imido group (preferably imido groups having 10 or less carbon atoms, e.g., N-succinimido, N-phthalimido), an alkoxycarbonylamino group (preferably alkoxycarbonylamino groups having 2 to 40 carbon atoms, e.g., methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino), a cycloalkyloxycarbonylamino group (preferably cycloalkyloxycarbonylamino groups having 4 to 40 carbon atoms, e.g., cyclohexyloxycarbonylamino), an aryloxycarbonylamino group (preferably aryloxycarbonylamino groups having 7 to 40 carbon atoms, e.g., phenoxycarbonylamino), a sulfonamido group (preferably sulfonamido groups having 1 to 40 carbon atoms, e.g., methanesulfonamido, buthanesulfonamido, benzenesulfonamido, hexadecanesulfonamido), a sulfamoylamino group (preferably sulfamoylamino groups having 1 to 40 carbon atoms, e.g., N,N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably azo groups having 1 to 40 carbon atoms, e.g., phenylazo), an alkylthio group (preferably alkylthio groups having 1 to 40 carbon atoms, e.g., ethylthio, octylthio), a cycloalkylthio group (preferably cycloalkylthio groups having 3 to 40 carbon atoms, e.g., cyclohexylthio), an arylthio group (preferably arylthio groups having 6 to 40 carbon atoms, e.g., phenylthio), a heterocyclic thio group (preferably heterocyclic thio groups having 1 to 40 carbon atoms wherein the heterocyclic moiety is the same as that of the above-described heterocyclic group, e.g., 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably alkylsulfinyl groups having 1 to 40 carbon atoms, e.g., dodecanesulfinyl), an arylsulfinyl group (preferably arylsulfinyl groups having 6 to 40 carbon atoms, e.g., benzenesulfinyl), an alkanesulfonyl group (preferably alkanesulfonyl groups having 1 to 40 carbon atoms, e.g., methanesulfonyl, octanesulfonyl), an arylsulfonyl group (preferably arylsulfonyl groups having 6 to 40 carbon atoms, e.g., benzenesulfonyl, 1-naphthalenesulfonyl), an alkoxysulfonyl group (preferably alkoxysulfonyl groups having 1 to 40 carbon atoms, e.g., methoxysulfonyl, ethoxysulfonyl), a cycloalkyloxysulfonyl group (preferably cycloalkyloxysulfonyl groups having 3 to 40 carbon atoms, e.g., cyclopropyloxysulfonyl), an aryloxysulfonyl group (preferably aryloxysulfonyl groups having 6 to 40 carbon atoms, e.g., phenoxysulfonyl, p-methylphenoxysulfonyl), a sulfamoyl group (preferably sulfamoyl groups having 32 or less carbon atoms, e.g., sulfamoyl, N,N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), a sulfo group, a phosphonyl group (preferably phosphonyl groups having 1 to 40 carbon atoms, e.g., phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), and a phosphinoylamino group (preferably phosphinoylamino groups having 2 to 40 carbon atoms, e.g., diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).
The compounds represented by formula (I) according to the present invention will be explained below.
In the foregoing formula (I), R1 and R2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Preferable specific examples of these groups are the same as those of the alkyl, cycloalkyl, alkenyl, aryl and heterocyclic groups, which are exemplified (enumerated) on the above-mentioned R40. R1 and R2 may be the same or different from each other. Each group of R1 and R2 may have a substituent thereon. Examples of the substituent include those exemplified on the above-mentioned R40. R1 and R2 may combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle. The nitrogen-containing heterocycle may be a saturated or unsaturated, or aromatic heterocyclic ring. The ring-constituting atom of said heterocycle is preferably selected from the group consisting of carbon, nitrogen, oxygen and sulfur atoms. Specific examples of the heterocycle include 1-pyrrolidinyl, 1-piperidinyl, morpholino, 2-oxymorpholino, thiomorpholino, 1,1-dioxothiomorpholino, piperadinyl, 1-pyrrolyl, pyrazolidinyl, indolyl, 1,4-dihydropyridine-1-yl, 2-oxymorpholino, 3-thiazolidine and 3-pyrroline-1-yl.
The above-mentioned nitrogen-containing heterocycle may have a substituent. Examples of the substituent include those exemplified on the above-mentioned R40.
Each of R1 and R2 is preferably an alkyl group, a cycloalkyl group, or an alkenyl group. In this case, the carbon number of these groups is preferably in the range of 1 to 10, more preferably in the range of 1 to 5.
Further, it is also preferable that R1 and R2 are combined with each other to form a nitrogen-containing heterocycle.
Preferable specific examples of the group represented by R1R2Nxe2x80x94, which is a partial structure of the formula (I), are shown below, but the present invention is not limited thereto. 
The group represented by R1R2Nxe2x80x94 is more preferably a morpholine-4-yl group, bis(2-propenyl)amino group, bis(methoxycarbonylmethyl)amino group, or bis(ethoxycarbonylmethyl)amino group, and among these, a bis(methoxycarbonylmethyl)amino group or bis(ethoxycarbonylmethyl)amino group is further preferable, and a bis(ethoxycarbonylmethyl)amino group is particularly preferable.
R3 represents an alkyl group, a cycloalkyl group or an alkenyl group. Preferable specific examples of these groups are the same as those of the alkyl, cycloalkyl and alkenyl groups, which are exemplified on the above-mentioned R40. Each group of R3 may have a substituent. Examples of the substituent include those exemplified on the above-mentioned R40.
Preferably R3 is a group represented by the following formula (II). 
In formula (II), R11 and R12 each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group. Preferable specific examples of these groups are the same as those of the alkyl, cycloalkyl and alkenyl groups, which are exemplified on the above-mentioned R40. R13, R14 and R15 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group. When R13, R14 and R15 each represent an alkyl group, a cycloalkyl group or an alkenyl group, preferable specific examples of these groups are the same as those of the alkyl, cycloalkyl and alkenyl groups, which are exemplified on the above-mentioned R40. Preferably R13, R14 and R15 each independently represent a hydrogen atom.
Z represents carbon atoms necessary to form a 5- to 8-membered ring, which ring may be substituted and may be a saturated or unsaturated ring. When the ring has a substituent thereon, examples of the substituent include those exemplified on the above-mentioned R40.
Examples of the ring which is formed together with Z include cyclopentane, cyclohexane, cycloheptane, cyclooctane and cyclohexene rings. The ring which is formed together with Z is preferably a 5- or 6-membered ring, more preferably a cyclohexane ring that may have a substituent.
R5 represents an alkyl group or an aryl group. Preferable specific examples of these groups are the same as those of the alkyl and aryl groups, which are exemplified on the above-mentioned R40. Each of the groups represented by R5 may further have a substituent. Examples of the substituent include those exemplified on the above-mentioned R40.
R5 is preferably an alkyl group. The alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, especially preferably 1 to 5 carbon atoms. Further preferably R5 is an unsubstituted alkyl group.
R4, R6, R7 and R8 each independently represent a hydrogen atom or a substituent, with the proviso that at least one of R4, R6, R7 and R8 represents a substituent. Preferable specific examples of the substituent are the same as those exemplified on the above-mentioned R40. The substituent represented by R4, R6, R7 or R8 may be further substituted by a substituent. Examples of said substituent include those exemplified on the above-mentioned R40.
In case where each of R4, R6, R7 and R8 represents a substituent, preferable examples of said substituent include an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a carbonamido group and a sulfonamido group. Among these groups, are preferred an alkyl group, a hydroxyl group, an alkoxy group, a carbonamido group and a sulfonamido group. An alkyl group and an alkoxy group are especially preferred.
However, two groups of R4 to R8, which adjoin each other, do not combine with each other to form any ring.
Preferable combination of group R5 and groups R4, R6, R7 and R8 is one in which R5 is an alkyl group and R7 is an alkyl group, and in this case more preferably R4, R6, and R8 each are a hydrogen atom. When R5 is a straight-chain alkyl group, R7 is preferably a branched-chain alkyl group, more preferably a tertiary alkyl group, and particularly preferably a t-butyl group.
Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto. 
The compound represented by formula (I) of the present invention can be synthesized with reference to the methods described, for example, in JP-A-7-48376 and JP-A-8-109172.
The compound represented by formula (I) of the present invention are useful as a dye-forming compound. The term xe2x80x9cdye-forming compoundxe2x80x9d herein used means a compound which is used for dye formation. Further, the term xe2x80x9cdyexe2x80x9d means a compound which has absorption in the range of infrared, near infrared to visible regions. The compound represented by formula (I) of the present invention is more preferably a compound capable of forming a dye which is used for image formation, or which is used as an image-constituting dye. Namely, said compound of the present invention is a dye-forming compound for image formation.
The dye can be easily obtained by reacting the compound of the present invention, represented by formula (I), with, for example, an oxidation product of an aromatic primary amine compound, especially a paraphenylenediamine derivative, an oxidation product of a hydrazine derivative, or a diazonium salt or a releaser of said salt. The foregoing method is more specifically described, for example, by Heinrich Zollinger, in Color Chemistry Syntheses, Properties and Applications of Organic Dyes and Pigments (Second, revised edition), VCH Verlagsgesellschaft mbH, Weinheim (Germany), 1991, or a literature referred to therein.
The dyes such as azomethine dyes and azo dyes, preformed by the compound represented by formula (I), may be used as a coloring matter or a dye for image formation. For example, the dyes are used as an ink dye for a printer of the ink jet system, and a dye for dye diffusion transfer system (DTR).
Further, said compound of the present invention may be incorporated in a system that has a mechanism capable of forming a dye, to form the dye in said system. A typical example in this case include the use of said compound of the invention as a coupler for a silver halide color photographic light-sensitive material.
However, the present invention is not limited to the above exemplified examples of use.
In the present invention, the compounds represented by formula (I) are preferably used as a coupler, more preferably as a cyan coupler, and most preferably used in a silver halide color light-sensitive material, especially in a silver halide color photographic light-sensitive material.
Use of the compound of the present invention in the silver halide color photographic light-sensitive material, which is the most preferable embodiment, is explained below.
The light-sensitive material of the present invention essentially has a support and thereon at least one layer containing the coupler according to the present invention, in which the layer containing the coupler according to the present invention is essentially a hydrophilic colloid layer on the support. An ordinary light-sensitive material is composed of at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one red-sensitive silver halide emulsion layer, which are coated on a support in this order. The layer configuration may be different from this order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned light-sensitive silver halide emulsion layers. A color reproduction owing to the subtractive color process can be performed by these light-sensitive emulsion layers incorporating therein silver halide emulsions each having sensitivity in each corresponding wavelengh region, and a color coupler cable of forming a dye each of which has a relationship of the complementary color with a light to which each of the silver halide emulsion layers is sensitive. However, the light-sensitive emulsion layer and the hue of color obtained by the color coupler may not be designed so as to have such a relationship. It is especially preferred to use the compound of the present invention as a cyan coupler in a red-sensitive silver halide emulsion layer. The content of the coupler according to the present invention in a light-sensitive material is generally in the range of 1xc3x9710xe2x88x923 mole to 1 mole, preferably in the range of 2xc3x9710xe2x88x923 mole to 5xc3x9710xe2x88x921 mole, per mole of silver halide in the same layer.
The coupler according to the present invention may be incorporated in a light-sensitive material by various known dispersion processes. It is preferred to use an oil-in-water dispersion process in which first a compound is dissolved in a high-boiling-point organic solvent (in combination with a low-boiling-point organic solvent as occasion demands), thereby forming a solution, and then the resulting solution is emulsified and dispersed in an aqueous gelatin solution, which is then added to a silver halide emulsion. Examples of the high-boiling-point organic solvent for use in the oil-in-water dispersion process are described in, for example, JP-A-5-313327, JP-A-5-323539, JP-A-5-323541, JP-A-6-258803, JP-A-8-262662, and U.S. Pat. No. 2,322,027. Further, the steps, effects and specific examples of latex polymers for impregnation, which are used in the latex dispersion process as one of polymer dispersion process, are described in, for example, U.S. Pat. No. 4,199,363, West German Patent Application (OLS) U.S. Pat. Nos. 2,541,274 and 2,541,230, JP-B-53-41091 (xe2x80x9cJP-Bxe2x80x9d means examined Japanese patent publication), and European Patent (laid open to public) No. 029104. Further, dispersion processes using an organic solvent-soluble polymer are described in, for example, PCT International Publication WO 88/00723 and JP-A-5-150420. Methacrylate-series or acrylamide-series polymers are preferred. In particular, the use of acrylamide-series polymers is preferred, in view of enhancing image fastness.
The term xe2x80x9chigh boiling pointxe2x80x9d herein used means a boiling point of 175xc2x0 C. or more at ordinary pressure.
Examples of the high-boiling-point solvent for use in the present invention are described in, for example, U.S. Pat. No. 2,322,027. Specific examples of the high-boiling-point organic solvent having a boiling point of 175xc2x0 C. or more at ordinary pressure include phthalic acid esters {e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-amylphenyl) phthalate, bis(2,4-di-tert-amylphenyl) iso-phthalate, bis(1,1-di-ethylpropyl)phthalate}, esters of phosphoric acid or phosphonic acid (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethlhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate), amides (e.g., N,N-diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), sulfonamides (e.g., N-butylbenzenesulfonamide), alcohols and phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g., bis-(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributylate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g., N,N-dibutyl-2-butory-5-tert-octylaniline), hydrocarbones (e.g., paraffin, dodecylbenzene, diisopropylnaphthalate), and chlorinated paraffins. In particular, the foregoing phosphoric acid esters, and hydrogen-providing compounds described in JP-A-6-258803 and JP-A-8-262662 are preferably used, since they help to provide an excellent hue of dye.
In order to reduce a load to environment, it is preferred to use compounds described in European Patent Nos. EP-969320A1 and EP-969321A1, in place of the foregoing phthalic acid esters. In addition to the above-mentioned compounds, tributyl citrate, pentaglycelol triesters and the like may be used.
The dielectric constant of the high-boiling-point organic solvent varies depending on the purpose for use, but it is preferably in the range of 2.0 to 7.0, more preferably in the range of 3.0 to 6.0.
Further, as an auxiliary solvent, an organic solvent having a boiling point of 30xc2x0 C. or more, preferably in the range of 50xc2x0 C. to about 160xc2x0 C. may be used. Typical examples of the auxiliary solvent include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
All or a part of the auxiliary solvent may be removed from an emulsified dispersion by means of a vacuum distillation, a noodle washing, an ultrafiltration, or the like, as occasion demands for the purpose of improving storage stability with the lapse of time in the state of the emulsified dispersion, or inhibiting a change in photographic properties or improving stability with the lapse of time of the final coating composition in which the emulsified dispersion is mixed with a silver halide emulsion.
The average particle size of the oleophilic fine particle dispersion as obtained in the above is preferably in the range of 0.001 to 1.0 xcexcm, more preferably in the range of 0.05 to 0.30 xcexcm, and most preferably in the range of 0.08 to 0.20 xcexcm. The average particle size can be determined with a measuring device such as COULTER SUBMICRON PARTICLE ANALYZER model N4 (Trade name, made by Coulter Electronics Co., Ltd.). If the average particle size of the oleophilic fine-particle dispersion is too large, such problems easily arise that a color-formation efficiency of a coupler is lessened, or gloss on the surface of a light-sensitive material deteriorates. In contrast, if the average particle size is too small, viscosity of the dispersion increases and consequently handling becomes difficult at the time of production.
The amount to be used (in terms of weight ratio) of a dispersion of oleophilic fine particles composed of a coupler according to the present invention to a dispersion medium is preferably in the range of 2 to 0.1, more preferably in the range of 1.0 to 0.2, per 1 part of the dispersion medium. Examples of the dispersion medium include hydrophilic polymers, such as gelatin which is a typical example, and in addition thereto mention can be made of polyvinyl alcohol. The oleophilic fine-particle dispersion may contain various compounds, together with the coupler according to the present invention, in accordance with the purpose of use.
Known additives may be used with the coupler represented by formula (I) according to the present invention, for the purpose of improving both image fastness and processing-stability, and adjusting a hue.
For example, in order to improve light fastness, compounds described in JP-A-5-150426, JP-A-5-150424 and JP-A-5-150423 may be used. In particular, when a compound described in JP-A-5-150424 and a compound described in JP-A-5-150423 are used in combination, they exhibit an outstanding improvement effect. Further, for the purpose of improving both the light fastness at a low-coloring density part and the light stain at a white ground in particular, use of a cyan coupler described in JP-A-5-204110 in combination with the cyan coupler according to the present invention, or use of a compound described in U.S. Pat. No. 4,797,350, exhibits an outstanding improvement effect.
Further, it is preferred to use the compound of the present invention, in combination with cyan couplers represented by formula (ADF) described in JP-A-10-333297, as well as in combination with vinyl compounds represented by formula (II), aniline derivatives that have an oxygen-nitrogen bond or that are substituted with an alkoxy group, represented by formula (III), nondiffusion phenidone derivatives represented by formula (IV), nondiffusion carboxylic acids represented by formula (V), nondiffusion arylcarbamoyl derivatives represented by formula (VI), arylamide derivatives represented by formula (VII), and cyclicimide derivatives represented by formula (VIII), each of which are described in JP-A-11-258748. Explanation about each of the foregoing formulae, exemplified specific compounds thereof, and descriptions of synthetic methods and application methods, each of which are described in the above two patent publications, are entirely applied to the present invention. Therefore, these descriptions are incorporated herein into the present specification as a part thereof by reference.
In addition, polymers described in JP-A-8-62797, JP-A-9-171240 and JP-A-9-329861 are preferably used in a hydrophilic colloid layer, in view of inhibiting blix discoloration (leuco dye reciprocity failure) due to a bleaching solution or a bleach-fixing solution.
Compounds for improving dye image stability, such as those described in European Patent No.0277589 A2, are preferably used together with the couplers in the light-sensitive material of the present invention. In particular, it is preferable for such compounds to be used in combination with the pyrrolotriazole coupler represented by formula (I) according to the present invention and a pyrazoloazole coupler.
That is, two kinds of compounds described in the foregoing patent specifications, i.e., compounds of one kind which can produce chemically inert, substantially colorless compounds, by combining chemically with an aromatic amine developing agent remaining after color development processing and/or compounds of the other kind which can produce chemically inert, substantially colorless compounds, by combining chemically with an oxidized aromatic amine color-developing agent remaining after color development processing, are preferably used in combination or singly. By the use of these compounds, occurrence of stain which is due to formation of color dye via the reaction between the coupler and the unoxidized or oxidized color-developing agent remaining in the processed photographic film, and occurrence of other side effects, upon storage after photographic processing, can be inhibited effectively.
Other conventionally known photographic materials and additives may be used in the silver halide photographic light-sensitive material of the present invention.
For example, as a photographic support (base), a transmissive type support and a reflective type support may be used. As the transmissive type support, it is preferred to use transparent supports, such as a cellulose nitrate film, and a transparent film of polyethyleneterephthalate, or a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), or a polyester of NDCA, terephthalic acid and EG, provided thereon with an information-recording layer such as a magnetic layer. As the reflective type support, it is especially preferable to use a reflective support having a substrate laminated thereon with a plurality of polyethylene layers or polyester layers (water-proof resin layers or laminate layers), at least one of which contains a white pigment such as titanium oxide.
A more preferable reflective support for use in the present invention is a support having a paper substrate provided with a polyolefin layer having fine holes, on the same side as silver halide emulsion layers. The polyolefin layer may be composed of multi-layers. In this case, it is more preferable for the support to be composed of a fine hole-free polyolefin (e.g., polypropylene, polyethylene) layer adjacent to a gelatin layer on the same side as the silver halide emulsion layers, and a fine hole-containing polyolefin (e.g., polypropylene, polyethylene) layer closer to the paper substrate. The density of the multi-layer or single-layer of polyolefin layer(s) existing between the paper substrate and photographic constituting layers is preferably in the range of 0.40 to 1.0 g/ml, more preferably in the range of 0.50 to 0.70 g/ml. Further, the thickness of the multi-layer or single-layer of polyolefin layer(s) existing between the paper substrate and photographic constituting layers is preferably in the range of 10 to 100 xcexcm, more preferably in the range of 15 to 70 xcexcm. Further, the ratio of thickness of the polyolefin layer(s) to the paper substrate is preferably in the range of 0.05 to 0.5, more preferably in the range 0.1 to 0.2.
Further, it is also preferable for enhancing rigidity (mechanical strength) of the reflective support, by providing a polyolefin layer on the surface of the foregoing paper substrate opposite to the side of the photographic constituting layers, i.e., on the back surface of the paper substrate. In this case, it is preferable that the polyolefin layer on the back surface be polyethylene or polypropylene, the surface of which is matted, with the polypropylene being more preferable. The thickness of the polyolefin layer on the back surface is preferably in the range of 5 to 50 xcexcm, more preferably in the range of 10 to 30 xcexcm, and further the density thereof is preferably in the range of 0.7 to 1.1 g/ml. As to the reflective support for use in the present invention, preferable embodiments of the polyolefin layer provide on the paper substrate include those described in JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, JP-A-11-65024, European Patent Nos. 0880065 and 0880066.
Further, it is preferred that the above-described water-proof resin layer contains a fluorescent whitening agent. Further, the fluorescent whitening agent also may be dispersed in a hydrophilic colloid layer of the light-sensitive material. Preferred fluorescent whitening agents which can be used, include benzoxazole series, coumarin series, and pyrazoline series compounds. Further, fluorescent whitening agents of benzoxazolylnaphthalene series and benzoxazolylstilbene series are more preferably used. The amount of the fluorescent whitening agent to be used is not particularly limited, and preferably in the range of 1 to 100 mg/m2. When a fluorescent whitening agent is mixed with a water-proof resin, a mixing ratio of the fluorescent whitening agent to be used in the water-proof resin is preferably in the range of 0.0005 to 3% by mass, and more preferably in the range of 0.001 to 0.5% by mass of the resin.
Further, a transmissive type support or the foregoing reflective type support each having coated thereon a hydrophilic colloid layer containing a white pigment may be used as the reflective type support.
Furthermore, a reflective type support having a mirror plate reflective metal surface or a secondary diffusion reflective metal surface may be employed as the reflective type support.
As the support for use in the light-sensitive material of the present invention, a support of the white polyester type, or a support provided with a white pigment-containing layer on the same side as the silver halide emulsion layer, may be adopted for display use. Further, it is preferable for improving sharpness that an antihalation layer be provided on the silver halide emulsion layer side or the reverse side of the support. In particular, it is preferable that the transmission density of support be adjusted to the range of 0.35 to 0.8 so that a display may be enjoyed by means of both transmitted and reflected rays of light.
In the light-sensitive material of the present invention, in order to improve, e.g., the sharpness of an image, a dye (particularly an oxonole-series dye) that can be discolored by processing, as described in European Patent No. 0,337,490 A2, pages 27 to 76, is preferably added to the hydrophilic colloid layer such that an optical reflection density at 680 nm in the light-sensitive material is 0.70 or more. It is also preferable to add 12% by mass or more (more preferably 14% by mass or more) of titanium oxide that is surface-treated with, for example, dihydric to tetrahydric alcoholes (e.g., trimethylolethane) to a water-proof resin layer of the support.
The light-sensitive material of the present invention preferably contains, in their hydrophilic colloid layers, dyes (particularly oxonole dyes and cyanine dyes) that can be discolored by processing, as described in European Patent No. 0337490 A2, pages 27 to 76, in order to prevent irradiation or halation or enhance safelight safety (immunity). Further, dyes described in European Patent No. 0819977 are also preferably used in the present invention.
Among these water-soluble dyes, some deteriorate color separation or safelight safety when used in an increased amount. Preferable examples of the dye which can be used and which does not deteriorate color separation include water-soluble dyes described in JP-A-5-127324, JP-A-5-127325 and JP-A-5-216185.
In the present invention, it is possible to use a colored layer which can be discolored during processing, in place of the water-soluble dye, or in combination with the water-soluble dye. The colored layer capable of being discolored with a processing to be used may contact with a light-sensitive emulsion layer directly, or indirectly through an interlayer containing an agent for preventing color-mixing during processing, such as gelatin and hydroquinone. The colored layer is preferably provided as a lower layer (closer to a support) with respect to the emulsion layer which develops the same primary color as the color of the colored layer. It is possible to provide colored layers independently, each corresponding to respective primary colors. Alternatively, only one layer selected from them may be provided. In addition, it is possible to provide a colored layer subjected to coloring so as to match a plurality of primary-color regions. About the optical reflection density of the colored layer, it is preferred that at the wavelength which provides the highest optical density in a range of wavelengths used for exposure (a visible light region from 400 nm to 700 nm for an ordinary printer exposure, and the wavelength of the light generated from the light source in the case of scanning exposure), the optical density is within the range of 0.2 to 3.0, more preferably 0.5 to 2.5, and particularly preferably 0.8 to 2.0.
The colored layer described above may be formed by a known method. For example, there are a method in which a dye in a state of a dispersion of solid fine particles is incorporated in a hydrophilic colloid layer, as described in JP-A-2-282244, from page 3, upper right column to page 8, and JP-A-3-7931, from page 3, upper right column to page 11, left under column; a method in which an anionic dye is mordanted in a cationic polymer, a method in which a dye is adsorbed onto fine grains of silver halide or the like and fixed in the layer, and a method in which a colloidal silver is used as described in JP-A-1-239544. As to a method of dispersing fine-powder of a dye in solid state, for example, JP-A-2-308244, pages 4 to 13 describes a method in which solid fine particles of dye which is at least substantially water-insoluble at the pH of 6 or less, but at least substantially water-soluble at the pH of 8 or more, are incorporated. The method of mordanting anionic dyes in a cationic polymer is described, for example, in JP-A-2-84637, pages 18 to 26. U.S. Pat. Nos. 2,688,601 and 3,459,563 disclose a method of preparing a colloidal silver for use as a light absorber. Among these methods, preferred are the methods of incorporating fine particles of dye and of using a colloidal silver.
Silver halide grains in the silver halide emulsion which can be used in the present invention, are preferably cubic or tetradecahedral crystal grains substantially having {100} planes (these grains may be rounded at the apexes thereof and further may have planes of higher order), or octahedral crystal grains. Further, a silver halide emulsion in which the proportion of tabular grains having an aspect ratio of 2 or more and composed of {100} or {111} planes accounts for 50% or more in terms of the total projected area, can also be preferably used. The term xe2x80x9caspect ratioxe2x80x9d means the value obtained by dividing the diameter of the circle having an area equivalent to the projected area of an individual grain by the thickness of the grain. In the present invention, cubic grains, or tabular grains having {100} planes as major faces, or tabular grains having {111} planes as major faces are preferably used.
As a silver halide emulsion which can be used in the present invention, for example, silver chloride, silver bromide, silver iodobromide, or silver chloro(iodo)bromide emulsions may be used. It is preferable for a rapid processing to use a silver chloride or silver chlorobromide emulsion having a silver chloride content of 95 mole % or greater, more preferably a silver halide emulsion having a silver chloride content of 98 mole % or greater. Especially preferred of these silver halide emulsions are those containing silver chloride grains having a silver bromide localized phase on the surface thereof, since both a high sensitivity and a stabilization of photographic properties are attained. Further, it is also preferred to use silver halide grains having in their shell parts a silver iodochloride phase of 0.01 to 0.50 mole %, more preferably 0.10 to 0.40 mole %, per mole of the total silver, in view of a high sensitivity and an excellent high illumination intensity exposure suitability.
The silver bromide localized phase is preferably formed by epitaxial growth of the localized phase having a total silver bromide content of at least 10 mole % in the silver bromide localized phase. A silver bromide content of the silver bromide localized phase is preferably in the range of 10 to 60 mole %, and most preferably in the range of 20 to 50 mole %. The silver bromide localized phase is preferably composed of silver having population of 0.1 to 5 mole %, more preferably 0.3 to 4 mole % to the molar amount of entire silver which constitutes silver halide grains for use in the present invention. The silver bromide localized phase is preferably doped with complex ions of metals of Group VIII, such as iridium (III) chloride, iridium (III) bromide, iridium (IV) chloride, sodium hexachloroiridate (III), potassium hexachloroiridate (IV), hexaammineiridium (IV) salts, trioxalatoiridium (III) salt, and trioxalatoiridium (IV) salt. The amount of these compounds to be added can be varied in a wide range depending on the purposes, and it is preferably in the range of 10xe2x88x929 to 10xe2x88x922 mole per mole of silver halide.
In a silver halide emulsion for use in the present invention, various kinds of polyvalent metal ion impurities other than iridium may be incorporated, during grain formation or in the course of physical ripening of the emulsion. As for examples of the impurities to be used, salts or complex salts of metals of Group VIII of the periodic table, such as iron, ruthenium, osmium, rhenium, rhodium, cadmium, zinc, lead, copper and thallium may be used in combination thereof. In the present invention, compounds of metals such as iron, ruthenium, osmium and rhenium, which have at least four cyano ligands, are particularly preferred, since a high illumination intensity sensitivity is further enhanced and latent image sensitization is also inhibited. Iridium compounds provide an outstanding effect on the high-illumination intensity exposure suitability. The amount of these compounds to be added can be varied in a wide range depending on the purposes, and it is preferably in the range of 10xe2x88x929 mole to 10xe2x88x922 mole, per mole of silver halide.
The silver halide grains contained in the silver halide emulsion for use in the present invention have an average grain size (the grain size herein means the diameter of the circle equivalent to the projected area of the grain, and the number average is taken as the average grain size) of preferably from 0.1 xcexcm to 2 xcexcm.
With respect to the distribution of sizes of these grains, so called monodisperse emulsion having a variation coefficient (the value obtained by dividing the standard deviation of the grain size distribution by the average grain size) of 20% or less, more preferably 15% or less, and further preferably 10% or less, is preferred. For obtaining a wide latitude, it is also preferred to blend the above-described monodisperse emulsions in the same layer or to form a multilayer structure using the monodisperse emulsions.
Various compounds or precursors thereof can be included in the silver halide emulsion for use in the present invention to prevent fogging from occurring or to stabilize photographic performance during manufacture, storage or photographic processing of the photographic material. Specific examples of compounds useful for the above purposes are disclosed in JP-A-62-215272, pages 39 to 72, and they can be preferably used. In addition, 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residual group has at least one electron-attractive group) disclosed in European Patent No. 0447647 can also be preferably used.
Further, in order to enhance storage stability of the silver halide emulsion for use in the present invention, it is also preferred in the present invention to use hydroxamic acid derivatives described in JP-A-11-109576; cyclic ketones having a double bond adjacent to a carbonyl group, both ends of said double bond being substituted with an amino group or a hydroxyl group, as described in JP-A-11-327094 (particularly compounds represented by formula (S1); the description at paragraph Nos. 0036 to 0071 of JP-A-11-327094 is incorporated herein by reference); sulfo-substituted catecols and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts of these acids); water-soluble reducing agents represented by formula (I), (II), or (III) of JP-A-11-102045; hydroxylamines represented by formula (A) described in U.S. Pat. No. 5,556,741 (the description at column 4 line 56 to column 11 line 22 of U.S. Pat. No. 5,556,741 is also applied to the present invention, and therefore incorporated herein by reference).
Spectral sensitization can be carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the light-sensitive emulsion in each layer of the photographic material of the present invention.
Spectral sensitizing dyes which are used in the photographic material of the present invention for spectral sensitization of blue, green and red light regions include, for example, those disclosed by F. M. Harmer, in Heterocyclic Compoundsxe2x80x94Cyanine Dyes and Related Compounds, John Wiley and Sons, New York, London (1964). Specific examples of compounds and spectral sensitization processes that are preferably used in the present invention include those described in JP-A-62-215272, from page 22, right upper column to page 38. In addition, the spectral sensitizing dyes described in JP-A-3-123340 are very preferred as red-sensitive spectral sensitizing dyes for silver halide emulsion grains having a high silver chloride content from the viewpoint of stability, adsorption strength and the temperature dependency of exposure, and the like.
The amount of these spectral sensitizing dyes to be added can be varied in a wide range depending on the occasion, and it is preferably in the range of 0.5xc3x9710xe2x88x926 mole to 1.0xc3x9710xe2x88x922 mole, more preferably in the range of 1.0xc3x9710xe2x88x926 mole to 5.0xc3x9710xe2x88x923 mole, per mole of silver halide.
The silver halide emulsion that can be used in the present invention are generally chemically sensitized. Chemical sensitization can be performed by utilizing a sulfur sensitization, represented by the addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, and reduction sensitization, each singly or in combination thereof. Compounds that are preferably used for chemical sensitization include those described in JP-A-62-215272, from page 18, right lower column to page 22, right upper column. Of these chemical sensitization, gold-sensitized silver halide emulsion are particularly preferred, since a change in photographic properties which occurs when scanning exposure to laser beams or the like is conducted, can be further reduced by gold sensitization. In order to conduct gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates, gold thiosulfates, and colloidal gold sulfide may be used. The amount of these compounds to be added can be varied in a wide range depending on the occasion, and it is generally in the range of 5xc3x9710xe2x88x927 mole to 5xc3x9710xe2x88x923 mole, preferably in the range of 1xc3x9710xe2x88x926 mole to 1xc3x9710xe2x88x924 mole, per mole of silver halide. In the present invention, gold sensitization may be used in combination with other sensitizing methods, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a noble metal compound other than gold compounds. In particular, the combination of gold sensitization and sulfur sensitization is preferable.
The silver halide photographic light-sensitive material of the present invention can be used for a color negative film, a color positive film, a color reversal film, a color reversal photographic printing paper, a color photographic printing paper and the like. Among these materials, the light-sensitive material of the present invention is preferably used for a color photographic printing paper.
The color photographic printing paper preferably has at least one yellow color-forming silver halide emulsion layer, at least one magenta color-forming silver halide emulsion layer, and at least one cyan color-forming silver halide emulsion layer, on a support. Generally, these silver halide emulsion layers are in the order, from the support, of the yellow color-forming silver halide emulsion layer, the magenta color-forming silver halide emulsion layer and the cyan color-forming silver halide emulsion layer.
However, another layer arrangement which is different from the above, may be adopted.
In the present invention, a yellow coupler-containing silver halide emulsion layer may be disposed at any position on a support. However, in the case where silver halide tabular grains are contained in the yellow coupler-containing layer, it is preferable that the yellow coupler-containing layer be positioned more apart from a support than at least one of a magenta coupler-containing silver halide emulsion layer and a cyan coupler-containing silver halide emulsion layer. Further, it is preferable that the yellow coupler-containing silver halide emulsion layer be positioned most apart from a support of other silver halide emulsion layers, from the viewpoint of color-development acceleration, desilvering acceleration, and reduction in a residual color due to a sensitizing dye. Further, it is preferable that the cyan coupler-containing silver halide emulsion layer be disposed in the middle of other silver halide emulsion layers, from the viewpoint of reduction in a blix fading. On the other hand, it is preferable that the cyan coupler-containing silver halide emulsion layer be the lowest layer, from the viewpoint of reduction in a light fading. Further, each of a yellow-color-forming layer, a magenta-color-forming layer and a cyan-color-forming layer may be composed of two or three layers. It is also preferable that a color forming layer be formed by disposing a silver halide emulsion-free layer containing a coupler in adjacent to a silver halide emulsion layer, as described in, for example, JP-A-4-75055, JP-A-9-114035, JP-A-10-246940, and U.S. Pat. No. 5,576,159.
Preferred examples of silver halide emulsions and other materials (additives or the like) for use in the present invention, photographic constitutional layers (arrangement of the layers or the like), and processing methods for processing the photographic materials and additives for processing are disclosed in JP-A-62-215272, JP-A-2-33144 and European Patent No. 0355660 A2. Particularly, those disclosed in European Patent No. 0355660 A2 are preferably used. Further, it is also preferred to use silver halide color photographic light-sensitive materials and processing methods therefor disclosed in, for example, JP-A-5-34889, JP-A-4-359249, JP-A-4-313753, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854, JP-A-1-158431, JP-A-2-90145, JP-A-3-194539, JP-A-2-93641 and European Patent Publication No. 0520457 A2.
In particular, as the above-described reflective support and silver halide emulsion, as well as the different kinds of metal ions to be doped in the silver halide grains, the storage stabilizers or antifogging agents of the silver halide emulsion, the methods of chemical sensitization (sensitizers), the methods of spectral sensitization (spectral sensitizers), the cyan, magenta, and yellow couplers and the emulsifying and dispersing methods thereof, the dye stability-improving agents (stain inhibitors and discoloration inhibitors), the dyes (coloring layers), the kinds of gelatin, the layer structure of the light-sensitive material, and the film pH of the light-sensitive material, those described in the patent publications as shown in the following Table 1 are preferably used in the present invention.
As other cyan, magenta and yellow couplers which can be used in combination in the present invention, those disclosed in JP-A-62-215272, page 91, right upper column line 4 to page 121, left upper column line 6, JP-A-2-33144, page 3, right upper column line 14 to page 18, left upper column bottom line, and page 30, right upper column line 6 to page 35, right under column, line 11, European Patent No. 0355,660 (A2), page 4 lines 15 to 27, page 5 line 30 to page 28 bottom line, page 45 lines 29 to 31, page 47 line 23 to page 63 line 50, are also advantageously used.
Further, it is preferred for the present invention to add compounds represented by formula (II) or (III) in WO 98/33760 and compounds represented by formula (D) described in JP-A-10-221825.
These are further specifically explained below.
As the cyan coupler which can be used together with the cyan coupler according to the present invention, the use in combination with phenol-series or naphthol-series cyan couplers is preferred as mentioned above. For example, cyan couplers represented by formula (ADF) described in JP-A-10-333297 are preferred.
As cyan couplers other than the foregoing cyan couplers, which are preferably used in combination, there are pyrroloazole cyan couplers described in European Patent Nos. 0488248 and 0491197 (A1), 2,5-diacylaminophenol couplers described in U.S. Pat. No. 5,888,716, pyrazoloazole cyan couplers having an electron-withdrawing group or a hydrogen-bond group at the 6-position, described in U.S. Pat. Nos. 4,873,183 and 4,916,051, and particularly pyrazoloazole cyan couplers having a carbamoyl group at the 6-position, described in JP-A-8-171185, JP-A-8-311360 and JP-A-8-339060.
In addition, the cyan coupler according to the present invention can also be used together with a diphenylimidazole-series cyan coupler described in JP-A-2-33144; as well as a 3-hydroxypyridine-series cyan coupler (particularly a 2-equivalent coupler formed by allowing a 4-equivalent coupler of a coupler (42), to have a chlorine splitting-off group, and couplers (6) and (9), enumerated as specific examples are particularly preferable) described in EP 0333185 A2; a cyclic active methylene-series cyan coupler (particularly couplers 3, 8, and 34 enumerated as specific examples are particularly preferable) described in JP-A-64-32260; a pyrrolopyrozole cyan coupler described in European Patent No. 0456226 A1; or a pyrroloimidazole cyan coupler described in European Patent No. 0484909.
As yellow couplers, also preferably used in the present invention are acylacetamide yellow couplers in which the acyl group has a 3-membered to 5-membered cyclic structure, such as those described in European Patent No. 0447969 A1; malondianilide yellow couplers having a cyclic structure, as described in European Patent No. 0482552 A1; pyrrol-2 or 3-yl or indol-2 or 3-yl carbonyl acetic acid anilide-series couplers, as described in European Patent (laid open to public) Nos. 953870 A1, 953871 A1, 953872 A1, 953873 A1, 953874 A1 and 953875 A1; acylacetamide yellow couplers having a dioxane structure such as those described in U.S. Pat. No. 5,118,599, in addition to the compounds described in the above-mentioned table. Above all, acylacetamide yellow couplers in which the acyl group is an 1-alkylcyclopropane-1-carbonyl group, and malondianilide yellow couplers in which one anilide constitute an indoline ring are especially preferably used. These couplers may be used singly or as combined.
The magenta couplers that can be used in the present invention are 5-pyrazolone magenta couplers and pyrazoloazole magenta couplers such as those described in the above-mentioned patent publications in the above Table. Among these, preferred are pyrazolotriazole couplers in which a secondary or tertiary alkyl group is directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole ring, such as those described in JP-A-61-65245; pyrazoloazole couplers having a sulfonamido group in its molecule, such as those described in JP-A-61-65246; pyrazoloazole couplers having an alkoxyphenylsulfonamido ballasting group, such as those described in JP-A-61-147254; and pyrazoloazole couplers having an alkoxy or aryloxy group at the 6-position, such as those described in European Patent Nos. 0226849 A2 and 0294785 A, in view of the hue and stability of image to be formed therefrom and color-forming property of the couplers.
Particularly as the magenta coupler, pyrazoloazole couplers represented by formula (M-I) described in JP-A-8-122984 are preferred. The descriptions of paragraph Nos. 0009 to 0026 of the patent publication JP-A-8-122984 are entirely applied to the present invention and therefore are incorporated in the specification of this application as a part thereof by reference.
In addition, pyrazoloazole couplers having a steric hindrance group at both the 3- and 6-positions, as described in European Patent Nos. 854384 and 884640, can also be preferably used.
It is preferred that magenta or yellow couplers, as well as the cyan coupler according to the present invention, are also pregnated into a loadable latex polymer (as described, for example, in U.S. Pat. No. 4,203,716) in the presence (or absence) of the high-boiling-point organic solvent described in the foregoing table, or they are dissolved in the presence (or absence) of the foregoing high-boiling-point organic solvent with a polymer insoluble in water but soluble in an organic solvent, and then emulsified and dispersed into an aqueous hydrophilic colloid solution.
Examples of the water-insoluble but organic solvent-soluble polymer which can be preferably used, include the homo-polymers and co-polymers as disclosed in U.S. Pat. No. 4,857,449, from column 7 to column 15 and WO 88/00723, from page 12 to page 30. The use of methacrylate-series or acrylamide-series polymers, especially acrylamide-series polymers are more preferable in view of color-image stabilization and the like.
In the present invention, known color mixing-inhibitors may be used. Among these compounds, those described in the following patent publications are preferred.
For example, high molecular weight redox compounds described in JP-A-5-333501; phenidone- or hydrazine-series compounds as described in, for example, WO 98/33760 and U.S. Pat. No. 4,923,787; and white couplers as described in, for example, JP-A-5-249637, JP-A-10-282615 and German Patent No. 19629142 A1, may be used. Particularly, in order to accelerate a developing speed by increasing the pH of a developing solution, redox compounds described in, for example, German Patent No. 19,618,786 A1, European Patent Nos. 0,839,623 A1 and 0,842,975 A1, German Patent No. 19,806,846 A1 and French Patent No. 2,760,460 A1, are also preferably used.
In the present invention, as an ultraviolet ray absorbent, it is preferred to use compounds having a high molar extinction coefficient and a triazine skeleton. Among these compounds, use can be made of those described, for example, in JP-A-46-3335, JP-A-55-152776, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-211813, JP-A-8-53427, JP-A-8-234364, JP-A-8-239368, JP-A-9-31067, JP-A-10-115898, JP-A-10-147577, JP-A-10-182621, German Patent No. 19,739,797A, European Patent No. 0,711,804 A and JP-T-8-501291 (xe2x80x9cJP-Txe2x80x9d means searched and published International patent application).
A combination of the cyan coupler represented by formula (I) according to the present invention and the above-described ultraviolet ray-absorbing agent having a triazine skeleton is particularly preferred. In this case, it is preferred to add said triazine-series ultraviolet ray absorbing agent in a light-insensitive layer located on a support, farther from the layer containing the cyan coupler represented by formula (I) according to the present invention, or/and in the same layer as said cyan coupler-containing layer.
As the binder or protective colloid which can be used in photographic layers to constitute the light-sensitive material of the present invention, gelatin is used advantageously, but another hydrophilic colloid can be used singly or in combination with gelatin. It is preferable for the gelatin for use in the present invention that the content of heavy metals, such as Fe, Cu, Zn and Mn, as impurities therein, be reduced to 5 ppm or below, more preferably 3 ppm or below.
Further, the amount of calcium contained in the light-sensitive material is preferably 20 mg/m2 or less, more preferably 10 mg/m2 or less, and most preferably 5 mg/m2 or less.
In the present invention, it is preferred to add an antibacterial (fungi-preventing) agent and antimold agent, as described in JP-A-63-271247, in order to destroy various kinds of molds and bacteria which propagate in a hydrophilic colloid layer and deteriorate the image.
Further, the pH of the film of the light-sensitive material is preferably in the range of 4.0 to 7.0, more preferably in the range of 4.0 to 6.5.
The light-sensitive material of the present invention can preferably be used, in a scanning exposure system using a cathode ray tube (CRT), in addition to the printing system using a usual negative printer.
The cathode ray tube exposure apparatus is simpler and more compact, and therefore less expensive than a laser-emitting apparatus. Further, optical axis and color (hue) can easily be adjusted.
In a cathode ray tube which is used for image-wise exposure, various light-emitting materials which emit a light in the spectral region, are used as occasion demands. For example, any one of red-light-emitting materials, green-light-emitting materials, blue-light-emitting materials, or a mixture of two or more of these light-emitting materials may be used. The spectral regions are not limited to the above red, green and blue, and fluorophoroes which can emit a light in a region of yellow, orange, purple or infrared can be used. Particularly, a cathode ray tube which emits a white light by means of a mixture of these light-emitting materials, is often used.
In the case where the light-sensitive material has a plurality of light-sensitive layers each having different spectral sensitivity distribution from each other and also the cathode ray tube has a fluorescent substance which emits light in a plurality of spectral regions, exposure to a plurality of colors may be carried out at the same time. Namely, a plurality of color image signals may be input into a cathode ray tube, to allow light to be emitted from the surface of the tube. Alternatively, a method in which an image signal of each of colors is successively input and light of each of colors is emitted in order, and then exposure is carried out through a film capable of cutting a color other than the emitted color, i.e., a surface successive exposure, may be used. Generally, among these methods the surface successive exposure is preferred from the viewpoint of high quality enhancement, because a cathode ray tube having a high resolving power can be used.
The light-sensitive material of the present invention can preferably be used in the digital scanning exposure system using monochromatic high density light, such as a gas laser, a light-emitting diode, a semiconductor laser, a second harmonic generation light source (SHG) comprising a combination of nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor laser as an excitation light source. It is preferred to use a semiconductor laser, or a second harmonic generation light source (SHG) comprising a combination of nonlinear optical crystal with a solid state laser or a semiconductor laser, to make a system more compact and inexpensive. In particular, to design a compact and inexpensive apparatus having a longer duration of life and high stability, use of a semiconductor laser is preferable; and it is preferred that at least one of exposure light sources would be a semiconductor laser.
When such a scanning exposure light source is used, the maximum spectral sensitivity wavelength of the light-sensitive material of the present invention can be arbitrarily set up in accordance with the wavelength of a scanning exposure light source to be used. Since oscillation wavelength of a laser can be made half, using a SHG light source obtainable by a combination of a nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor as an excitation light source, blue light and green light can be obtained. Accordingly, it is possible to have the spectral sensitivity maximum of a photographic material in normal three wavelength regions of blue, green and red.
The exposure time in such a scanning exposure is defined as the time necessary to expose the size of the picture element (pixel) with the density of the picture element being 400 dpi, and preferred exposure time is 10xe2x88x924 sec or less and more preferably 10xe2x88x926 sec or less.
The scanning exposure system which can preferably be used for the present invention is described in detail in the patent publications as shown in the above table.
With respect to the processing method of the photographic material of the present invention, processing materials and processing methods, as disclosed in JP-A-2-207250, from page 26, right under column, line 1 to page 34, right upper column, line 9, and JP-A-4-97355, from page 5, left upper column, line 17 to page 18, right under column, line 20, can be preferably applied. Further, as preservatives which are used in the developing solution, compounds described in the patent publications as shown in the above table are preferably used.
The present invention is preferably applied to a light-sensitive material having rapid processing suitability.
The term xe2x80x9ccolor-developing timexe2x80x9d as used herein means a period of time required from the beginning of dipping a light-sensitive material into a color developing solution until the light-sensitive material is dipped into a blix solution in the subsequent processing step. In the case where a processing is carried out using, for example, an autoprocessor, the color developing time is the sum total of a time in which a light-sensitive material has been dipped in a color developing solution (so-called xe2x80x9ctime in the solutionxe2x80x9d) and a time in which the light-sensitive material has been conveyed in air toward a bleach-fixing bath in the step subsequent to color development (so-called xe2x80x9ctime in the airxe2x80x9d). Likewise, the term xe2x80x9cblix timexe2x80x9d as used herein means a period of time required from the beginning of dipping a light-sensitive material into a blix solution until the light-sensitive material is dipped into a washing bath or a stabilizing bath in the subsequent processing step. Further, the term xe2x80x9cwashing or stabilizing timexe2x80x9d as used herein means a period of time required from the beginning of dipping a light-sensitive material into a washing solution or a stabilizing solution until the end of the dipping toward a drying step (so-called xe2x80x9ctime in the solutionxe2x80x9d).
In the present invention, the color-developing time is preferably 60 sec or less, more preferably from 50 sec to 6 sec, further preferably from 30 sec to 6 sec. Likewise, the blix time is preferably 60 sec or less, more preferably from 50 sec to 6 sec, further preferably from 30 sec to 6 sec. Further, the washing or stabilizing time is preferably 150 sec or less, more preferably from 130 sec to 6 sec.
Examples of a development method applicable to the photographic material of the present invention after exposure, include a conventional wet system, such as a development method using a developing solution containing an alkali agent and a developing agent, and a development method wherein a developing agent is incorporated in the photographic material and an activator solution, e.g., a developing agent-free alkaline solution is employed for the development, as well as a heat development system using no processing solution. In particular, the activator method using a developing agent-free alkaline solution is preferred over the other methods, because the processing solution contains no developing agent, thereby it enables easy management and handling of the processing solution and reduction in waste disposal load to make for environmental preservation.
The preferable developing agents or their precursors incorporated in the photographic materials in the case of adopting the activator method include the hydrazine compounds described in, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152693, JP-A-9-211814 and JP-A-9-160193.
Further, the processing method in which the photographic material reduced in the amount of silver to be applied undergoes the image amplification processing using hydrogen peroxide (intensification processing), can be employed preferably. In particular, it is preferably to apply this processing method to the activator method. Specifically, the image-forming methods utilizing an activator solution containing hydrogen peroxide, as disclosed in JP-A-8-297354 and JP-A-9-152695 can be preferably used.
Although the processing with an activator solution is generally followed by a desilvering step in the activator method, the desilvering step can be omitted in the case of applying the image amplification processing method to photographic materials having a reduced silver amount. In such a case, washing or stabilization processing can follow the processing with an activator solution to result in simplification of the processing process. On the other hand, when the system of reading the image information from photographic materials by means of a scanner or the like is employed, the processing form requiring no desilvering step can be applied, even if the photographic materials are those having a high silver amount, such as photographic materials for shooting.
The activator solution, desilvering solution (bleaching/fixing solution), washing solution and stabilizing solution for use in the present invention can contain known ingredients and can be used in conventional manners. Preferably, those described in Research Disclosure, Item 36544, pp. 536-541 (September 1994), and JP-A-8-234388 can be used in the present invention.
It is preferred to use a band stop filter, as described in U.S. Pat. No. 4,880,726, when the photographic material of the present invention is subjected to exposure with a printer. Color mixing of light can be excluded and color reproducibility is remarkably improved by the above means.
In the present invention, a yellow microdot pattern may be previously formed by pre-exposure before giving an image information, to thereby perform a copy restraint, as described in European Patent Nos. 0789270 A1 and 0789480 A1.
In case where the cyan coupler represented by formula (I) according to the present invention is applied to a color negative film, the description at paragraph Nos. 0115 to 0217 of JP-A-11-305396 is preferably applied thereto, and therefore said description is incorporated herein by reference.
Further, in case where the cyan coupler represented by formula (I) according to the present invention is applied to a color reversal film, the description at paragraph Nos. 0018 to 0021 of JP-A-11-84601 is preferably applied thereto, and therefore said description is incorporated herein by reference.
The silver halide color photographic light-sensitive material of the present invention exhibits a high color-forming property and an excellent hue and light-fastness of the dye image formed thereby. Further, the pyrrolotriazole compound of the present invention has said excellent photographic properties, and it is particularly useful as a dye-forming compound.
According to the novel pyrrolotriazole compound of the present invention, a dye having excellent hue and fastness to light can be obtained. Particularly, the pyrrolotriazole compound is useful as a dye-forming compound. When the pyrrolotriazole compound is used as a cyan coupler in a silver halide color photographic light-sensitive material, it exhibit such excellent effects that a high color-forming property is attained, the dye image obtained thereby is excellent in light-fastness, and also both a cyan hue with no color contamination and considerable improvement in processing color mixing are attained. The silver halide color photographic light-sensitive material of the present invention that contains the above-described compound is excellent in both color reproduction and light-fastness, and also has a high illumination intensity exposure suitability.